JP7117286B2 - Surface treatment agent and its manufacturing method - Google Patents

Description

TECHNICAL FIELD The present invention relates to a surface treatment agent and a method for producing the same, and in particular, a surface treatment agent containing a polymer useful as a release agent for rubber and resin including FRP, a water and oil repellent, a buffer, and a resin adhesion preventive. and its manufacturing method.

Conventionally, in order to exhibit surface functionality such as releasability, water and oil repellency, and low surface tension, fluorine-containing (meta- ) Acrylic polymers have been used as surface treatment agents (for example, Patent Document 1). In recent years, it has become a problem that compounds having a perfluoroalkyl group with 8 or more carbon atoms generate perfluorooctanoic acid (PFOA), perfluorooctane sulfonic acid (PFOS), etc. by decomposition after disposal. Substitution to compounds having 6 or less perfluoroalkyl groups is underway. However, when the number of carbon atoms is 6 or less, it does not exhibit crystallinity like a compound having a perfluoroalkyl group of 8 or more carbon atoms, so it has surface functionality such as releasability, water and oil repellency, and low surface tension. is a new problem. For example, when used as a release agent, a fluorine-containing polymer containing a perfluoroalkyl group with a carbon number of 6 or less does not have sufficient release performance (continuous release property) in one application (for example, , Patent Document 2).

Patent Document 3 discloses preparation of a cured film using a fluorine-containing copolymer having a fluorine content of 1% to 10% by mass and a surface modifier containing a condensed hydroxy fatty acid.

JP-A-03-256310 WO2009/119445 JP 2016-44210 A

An object of the present invention is to provide a surface treatment agent which is excellent in surface functionalities such as water/oil repellency, releasability, cushioning property, resin adhesion prevention property, and continuous releasability, and a method for producing the same.

The present invention provides the following surface treatment agent and method for producing the same.
Section 1. A surface treatment agent containing a polymer according to any one of the following (I) to (III):
(I) general formula (I)

[In the formula, R ^1A is H or a methyl group. N is 1-24. ]
A polymer containing as a repeating unit at least one monomer having a linear hydrocarbon group represented by
(II) general formula (II)

[In the formula, RF is a group represented by the following formula (1) or (2).

R ^1B is a divalent group having 2 to 50 carbon atoms. ^R2 is H or a methyl group. ]
A polymer comprising at least one fluorine-containing monomer represented by
(III) containing as repeating units at least one monomer having a linear hydrocarbon group represented by general formula (I) and at least one fluorine-containing monomer represented by general formula (II); A polymer containing 0% or more and 15% or less by mass of a fluorine monomer.
Section 2. Item 1. The surface treatment agent according to Item 1, which contains the following polymer (I) or (III):
(I) general formula (I)

[In the formula, R ^1A is H or a methyl group. N is 1-24. ]
A polymer containing as a repeating unit at least one monomer having a linear hydrocarbon group represented by
(III) containing as repeating units at least one monomer having a linear hydrocarbon group represented by general formula (I) and at least one fluorine-containing monomer represented by general formula (II); A polymer containing 0% or more and 15% or less by mass of a fluorine monomer.
Item 3. Item 1. The surface treatment agent according to item 1, which contains the polymer described in (II) below:
(II) general formula (II)

[In the formula, RF is a group represented by the following formula (1) or (2).

R ^1B is a divalent group having 2 to 50 carbon atoms. ^R2 is H or a methyl group. ]
A polymer containing at least one fluorine-containing monomer represented by as a repeating unit, the proportion of the fluorine-containing monomer being 15% or more by mass.
Section 4. the polymer is a monomer having a linear hydrocarbon group represented by general formula (I);
(A) a fluorine-containing monomer represented by the general formula (II), and/or
(B) A polymer containing a monomer having a hydrophilic group as a repeating unit. Item 3. The surface treating agent according to item 2.
Item 5. The polymer comprises a fluorine-containing monomer represented by general formula (II) and the following monomers (A) and/or (B) and/or (C):
(A) a monomer having a linear hydrocarbon group
(B) a monomer having a hydrophilic group
(C) at least one monomer selected from the group consisting of a monomer having a branched hydrocarbon group, a monomer having an alicyclic hydrocarbon group, a monomer containing a heteroaliphatic group or a heterocycle, and a monomer containing an aromatic ring; Item 4. The surface treating agent according to Item 3, which is a copolymer containing as a repeating unit.
Item 6. Item 6. The surface treatment agent according to any one of items 1 to 5, wherein the monomer having a linear hydrocarbon group represented by general formula (I) is one or two or more (meth)acrylates. .
Item 7. (A) a monomer having a linear hydrocarbon group is represented by general formula (I)

[In the formula, R ^1A is H or a methyl group. N is 1-24. ]
3. The surface treating agent according to Item 1 or 2, which is one or two or more (meth)acrylates represented by.
Item 8. Item 6. The surface treating agent according to item 4 or 5, wherein (B) the monomer having a hydrophilic group is a monomer having a hydroxyl group and/or a polyethylene oxide chain.
Item 9. Item 9. The surface treatment agent according to any one of Items 1 to 8, which is an aqueous emulsion.
Item 10. Item 10. The surface treating agent according to any one of Items 1 to 9, wherein the surface treating agent is a release agent.
Item 11. Item 11. The surface treating agent according to Item 10, wherein the surface treating agent is a release agent for BR rubber.
Item 12. Item 11. The surface treating agent according to Item 10, wherein the surface treating agent is a release agent for BR rubber or EPDM rubber.
Item 13. Item 11. The surface treating agent according to Item 10, wherein the surface treating agent is a release agent for thermosetting resin.
Item 14. Item 10. The surface treatment agent according to any one of Items 1 to 9, wherein the surface treatment agent is a water and oil repellent.
Item 15. Item 10. The surface treating agent according to any one of Items 1 to 9, wherein the surface treating agent is a buffering agent.
Item 16. Item 10. The surface treating agent according to any one of Items 1 to 9, wherein the surface treating agent is a resin adhesion inhibitor.
Item 17. The following general formula (I)

[In the formula, R ^1A is H or a methyl group. N is 1-24. ]
If necessary, a monomer having a linear hydrocarbon group represented by
(A) general formula (II)

[In the formula, RF is a group represented by the following formula (1) or (2).

R ^1B is a divalent group having 2 to 50 carbon atoms. ^R2 is H or a methyl group. ]
A fluorine-containing monomer represented by and / or
(B) a monomer having a hydrophilic group,
and wherein the proportion of the fluorine-containing monomer in the polymer is 0% or more and 15% or less by mass.
Item 18. The following structural general formula (II)

［式中、ＲＦは下記式（１）または（２）で示される基である。

[In the formula, RF is a group represented by the following formula (1) or (2).

R ^1B is a divalent group having 2 to 50 carbon atoms. ^R2 is H or a methyl group. ]
or homopolymerizing the fluorine-containing monomer represented by (A) a monomer having a linear hydrocarbon group and/or (B) a monomer having a hydrophilic group and/or (C) copolymerized with at least one monomer selected from the group consisting of a monomer having a branched hydrocarbon group, a monomer having an alicyclic hydrocarbon group, a monomer containing a heteroaliphatic group or a heterocycle, and a monomer containing an aromatic ring; and a step of obtaining a polymer having the fluorine-containing monomer as a repeating unit, wherein the proportion of the fluorine-containing monomer in the polymer is 15% by mass or more.

The surface treatment agent of the present invention is excellent in surface functionalities such as releasability, water and oil repellency, cushioning properties, resin adhesion prevention properties, and low surface tension. In particular, when used as a release agent for rubbers such as EPDM rubber and BR rubber, and for resins, it is useful as a release agent that exhibits excellent release properties and continuous release properties. In addition, the surface treatment agent of the present invention is also useful as a buffering agent and a resin adhesion preventive that are suitably used in resin molding and processing of composite materials such as FRP.

The outline of the releasability test of the vinyl ester resin using the test piece is shown. An embodiment of use as a buffering agent for the surface treatment agent of the present invention is shown.

(Meth)acrylate as used herein means acrylate and/or methacrylate.

The surface treatment agent of the present invention contains a polymer according to any one of (I) to (III) below:
(I) general formula (I)

[In the formula, R ^1A is H or a methyl group. N is 1-24. ]
A polymer containing as a repeating unit at least one monomer having a linear hydrocarbon group represented by
(II) general formula (II)

[In the formula, RF is a group represented by the following formula (1) or (2).

R ^1B is a divalent group having 2 to 50 carbon atoms. ^R2 is H or a methyl group. ]
A polymer comprising at least one fluorine-containing monomer represented by
(III) containing as repeating units at least one monomer having a linear hydrocarbon group represented by general formula (I) and at least one fluorine-containing monomer represented by general formula (II); A polymer containing 0% or more and 15% or less by mass of a fluorine monomer.

(Monomer having a linear hydrocarbon group)
As a monomer having a linear hydrocarbon group, general formula (I)

[In the formula, R ^1A is H or a methyl group. N is 1-24. ]
One or two or more (meth)acrylates having a linear hydrocarbon group represented by

R ^1A is H or a methyl group, preferably a methyl group.

N is 1-24, preferably 3-22, more preferably 5-22.

Specific examples of monomers having a linear hydrocarbon group include ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, Acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, Hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, heneicosyl (meth)acrylate, docosyl (meth)acrylate, tricosyl (meth)acrylate, tetracosyl ( Mention may be made of meth)acrylates, pentacosyl (meth)acrylates. A monomer having a linear hydrocarbon group may be used alone or in combination of two or more monomers. Hexyl methacrylate, lauryl acrylate, stearyl methacrylate, and lauryl methacrylate are preferred as monomers having a linear hydrocarbon group.

A monomer having a linear hydrocarbon group can be produced by a known method, or can be obtained as a commercial product.

(Fluorine-containing monomer represented by general formula (II))
The fluorine-containing monomer represented by general formula (II) is shown below:

[In the formula, RF is a group represented by the following formula (1) or (2).

R ^1B is a divalent group having 2 to 50 carbon atoms. ^R2 is H or a methyl group. ]
The divalent group having 2 to 50 carbon atoms represented by R ^1B may contain a heteroatom and is an aromatic group, a heteroaromatic group, a heterocyclic group, an aliphatic group, an alicyclic may be a base. Specific examples include the following groups.

—(CH ₂ ) _N1 — (N1=2 to 50)
-XY-(CH ₂ ) _N2 - (N2 = 2 to 43)
-X-(CH ₂ ) _N3 - (N3 = 1 to 44)
—CH ₂ CH ₂ (OCH ₂ CH ₂ ) _N4 — (N4=1 to 24)
-XCO(OCH ₂ CH ₂ ) _N5 - (N5 = 1 to 21)
(Wherein, X is an alkyl group having 1 to 3 carbon atoms (methyl, ethyl, propyl), an alkoxy group having 1 to 4 carbon atoms (methoxy, ethoxy, propoxy, butoxy, etc.), a halogen atom (F, CL, BR, phenylene, biphenylene or naphthylene optionally having 1 to 3 substituents selected from the group consisting of I) Y is -O-CO-, -CO-O-, -CONH- or -NHCO; - indicates.)
X is preferably 1,2-phenylene, 1,3-phenylene or 1,4-phenylene, particularly preferably 1,4-phenylene.

Particularly preferred divalent groups having 2 to 50 carbon atoms represented by R ^1B include divalent groups having the following structures.

—(CH ₂ ) _N1 — (N1=2 to 10)
—C ₆ H ₄ OCO(CH ₂ ) _N2 — (N2=2-10)
—C ₆ H ₄ (CH ₂ ) _N3 — (N3=1-10)
—CH ₂ CH ₂ (OCH ₂ CH ₂ ) _N4 — (N4=1-10)
_{-C6H4CO ( OCH2CH2} ) _N5- ( _N5 = 1 to 10)
R ² is H or a methyl group, preferably a methyl group.

A fluorine-containing monomer represented by general formula (II) can be produced by a known method. Only one type of the fluorine-containing monomer may be used, or two or more types may be mixed and used.

(Monomer having a hydrophilic group)
As the monomer having a hydrophilic group, a monomer having a hydroxyl group and/or a polyethylene oxide chain is preferable, such as a hydroxyalkyl (meth)acrylate having 1 to 4 carbon atoms, a polyethylene glycol mono(meth)acrylate, a polypropylene glycol mono(meth)acrylate. acrylates and the like, specifically 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, More preferred are 2-hydroxyethyl methacrylate and polyethylene glycol monomethacrylate. Commercial products of polyethylene glycol monomethacrylate include PE-90 and PE-200 manufactured by NOF Corporation.

A monomer having a hydrophilic group can be produced by a known method, or can be obtained as a commercial product.

(Monomer having a branched hydrocarbon group)
Specific examples of the monomer having a branched hydrocarbon group include isopropyl (meth) acrylate, SEC-butyl (meth) acrylate, isobutyl (meth) acrylate, TERT-butyl (meth) acrylate, isopentyl (meth) acrylate, isohexyl (meth)acrylate, isoheptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isononyl (meth)acrylate, isodecyl (meth)acrylate, isoundecyl (meth)acrylate, isododecyl (meth)acrylate, isotridecyl (meth)acrylate, Examples include isotetradecyl (meth)acrylate, isopentadecyl (meth)acrylate, isopalmityl (meth)acrylate, isoheptadecyl (meth)acrylate, isostearyl (meth)acrylate, and isoamyl (meth)acrylate. A monomer having a branched chain hydrocarbon group may be used alone or as a mixture of two or more monomers. Preferred monomers having a branched hydrocarbon group are 2-ethylhexyl methacrylate, isooctyl methacrylate, isodecyl methacrylate, isostearyl methacrylate, isononyl acrylate, TERT-butyl methacrylate, isobutyl methacrylate and isoamyl acrylate.

A monomer having a branched hydrocarbon group can be produced by a known method, or can be obtained as a commercial product.

(Monomer having an alicyclic hydrocarbon group)
Specific examples of monomers having an alicyclic hydrocarbon group include cyclopropyl (meth) acrylate, cyclobutyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclo Octyl (meth)acrylate, decalinyl (meth)acrylate, bicyclodecalinyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, adamantyl (meth)acrylate, Cyclohexyl (meth)acrylate, TERT-butylcyclohexyl (meth)acrylate may be mentioned. Monomers having an alicyclic hydrocarbon group may be used either singly or as a mixture of two or more monomers. Monomers having an alicyclic hydrocarbon group are preferably isobornyl methacrylate, isobornyl acrylate, dicyclopentanyl methacrylate, dicyclopentanyl acrylate, dicyclopentenyl methacrylate, dicyclopentenyl acrylate, adamantyl methacrylate, cyclohexyl methacrylate, TERT-butylcyclohexyl methacrylate.

A monomer having an alicyclic hydrocarbon group can be produced by a known method, or can be obtained as a commercial product.

(Monomer Containing Heteroaliphatic Group or Heterocycle)
Specific examples of monomers containing heteroaliphatic groups or heterocycles include tetrahydrofurfuryl (meth)acrylate, phenoxyethyl (meth)acrylate, methoxyethyl (meth)acrylate, ethylcarbitol (meth)acrylate, glycidyl ( meth) acrylate, methoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, cyclic trimethylolpropane formal (meth) acrylate, (3-ethyloxetane-3- yl)methyl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, unsaturated fatty acid hydroxyalkyl ester modified ε- Caprolactone, pentamethylpiperidinyl methacrylate, tetramethylpiperidinyl methacrylate, acryloylmorpholine, dimethylacrylamide, isopropylacrylamide, diethylacrylamide, dimethylaminopropylacrylamide and the like can be mentioned. A monomer containing a heteroaliphatic group or a heterocycle may be used alone or in combination of two or more monomers. Preferred monomers containing heteroaliphatic groups or heterocycles are glycidyl methacrylate, diethylacrylamide and ethyl carbitol acrylate.

Monomers containing heteroaliphatic groups or heterocycles can be prepared by known methods or can be obtained commercially.

(Monomer containing aromatic ring)
Specific examples of monomers containing an aromatic ring include phenyl (meth) acrylate, hydroxyphenyl (meth) acrylate, chlorophenyl (meth) acrylate, benzyl (meth) acrylate, methoxybenzyl (meth) acrylate, chlorobenzyl (meth) Acrylates, hydroxybenzyl (meth)acrylate, phenethyl (meth)acrylate, hydroxyphenethyl (meth)acrylate, phenoxymethyl (meth)acrylate, phenoxyethyl (meth)acrylate, dihydroxyphenethyl (meth)acrylate, furfuryl (meth)acrylate be able to. A monomer containing an aromatic ring may be used alone or in combination of two or more monomers. Preferred aromatic ring-containing monomers are benzyl methacrylate, benzyl acrylate and phenoxyethyl methacrylate.

A monomer containing an aromatic ring can be produced by a known method, or can be obtained as a commercial product.

<First preferred embodiment>
In the first preferred embodiment of the present invention, the polymer used in the surface treatment agent of the present invention contains, as an essential component, a monomer having a linear hydrocarbon group represented by general formula (I) as a repeating unit. .

The polymer of the first embodiment may be a homopolymer of a monomer having a linear hydrocarbon group represented by general formula (I), and a linear hydrocarbon represented by general formula (I) It may be a copolymer of a monomer having a group and another monomer. In the case of a homopolymer of a monomer having a linear hydrocarbon group represented by general formula (I), the proportion of the fluorine-containing monomer in the polymer is 0% by mass. Other monomers are
(A) a fluorine-containing monomer represented by the general formula (II);
(B) a monomer having a hydrophilic group. In a first embodiment, the polymer of the invention is
(1) Polymer of at least one monomer having a linear hydrocarbon group represented by general formula (I)
(2) A copolymer of at least one monomer having a linear hydrocarbon group represented by general formula (I) and at least one fluorine-containing monomer represented by general formula (II)
(3) A copolymer of at least one monomer having a linear hydrocarbon group represented by formula (I) and at least one monomer having a hydrophilic group
(4) at least one monomer having a linear hydrocarbon group represented by general formula (I), at least one fluorine-containing monomer represented by general formula (II), and at least one hydrophilic group; including copolymers of monomers with

In the first preferred embodiment, when the monomer having a straight chain hydrocarbon group of general formula (I) is used, the amount used is preferably 5 to 100% by mass with respect to the total amount of the resulting polymer. , more preferably 10 to 90%.

In a first preferred embodiment, the fluorine-containing monomer represented by the general formula (II) is preferably 0 to 15% by mass, more preferably 0 to 10% by mass, relative to the total amount of the polymer obtained, More preferably 5 to 10%.

In the first preferred embodiment, when a monomer having a hydrophilic group is used, the amount used is preferably 0 to 30% by mass, more preferably 0 to 20%, based on the total amount of the copolymer obtained. %.

<Second Preferred Embodiment>
In a second preferred embodiment of the present invention, the polymer used in the fluorine-based surface treatment agent of the present invention may be a homopolymer of a fluorine-containing monomer represented by general formula (II). and the following monomers (A) and/or (B) and/or (C):
(A) a monomer having a linear hydrocarbon group
(B) a monomer having a hydrophilic group
(C) at least one monomer selected from the group consisting of a monomer having a branched hydrocarbon group, a monomer having an alicyclic hydrocarbon group, a monomer containing a heteroaliphatic group or a heterocycle, and a monomer containing an aromatic ring; It may be a copolymer containing

In the polymer used in the second preferred embodiment, the proportion of the fluorine-containing monomer represented by general formula (II) is 15% or more, preferably more than 15% by mass.

In the second preferred embodiment, when the monomer having a linear hydrocarbon group of general formula (I) is used, the amount used is preferably 0 to 70 parts by mass, more preferably 0 to 50 parts by mass.

In the second preferred embodiment, the fluorine-containing monomer represented by the general formula (II) is usually 15 to 100 parts by mass, preferably 15 to 95 parts by mass, when the total amount of the resulting polymer is 100 parts by mass. and more preferably 15 to 90 parts by mass.

In the second preferred embodiment, when a monomer having a hydrophilic group is used, the amount used is preferably 0 to 30% by mass, more preferably 0 to 20%, based on the total amount of the resulting copolymer. %.

In the second preferred embodiment, when a monomer having a branched hydrocarbon group is used, the amount used is preferably 0 to 70% by mass, more preferably 0%, based on the total amount of the resulting copolymer. ~50%.

In the second preferred embodiment, when using a monomer having an alicyclic hydrocarbon group, the amount used is preferably 0 to 70% by mass, more preferably 0 to 50%.

In the second preferred embodiment, when a monomer containing a heteroaliphatic group or a heterocycle is used, the amount used is preferably 0 to 70% by mass, more preferably 0 to 70%, based on the total amount of the resulting copolymer. is 0-50%.

In the second preferred embodiment, when a monomer containing an aromatic ring is used, the amount used is preferably 0 to 70% by mass, more preferably 0 to 50%, based on the total amount of the copolymer obtained. is.

By setting the amount of the fluorine-containing monomer used to 15% or more by mass, it is possible to form an aqueous dispersion having excellent continuous releasability.

<Polymer of the present invention>
When the polymer of the present invention contains two or more monomers as raw materials, it may be a random copolymer or a block copolymer.

The weight average molecular weight (MW) of the homopolymer or copolymer of the present invention is generally 2,000-100,000, preferably 3,000-80,000, more preferably 5,000-60,000. The weight average molecular weight can be measured by the GPC method using standard polystyrene.

<Method for producing polymer>
In a first preferred embodiment, the polymer used in the surface treatment agent of the present invention is produced by homopolymerizing or copolymerizing at least one monomer having a linear hydrocarbon group represented by general formula (I). Alternatively, at least one monomer having a linear hydrocarbon group represented by general formula (I), (A) at least one fluorine-containing monomer represented by general formula (II), and/or (B) hydrophilic It may also be produced by copolymerizing a monomer containing at least one type having a functional group.

In a second preferred embodiment, the polymer used in the surface treatment agent of the present invention may be produced by homopolymerizing the fluorinated monomer of general formula (II). and (A) a monomer having a linear hydrocarbon group, and/or (B) a monomer having a hydrophilic group and/or (C) a monomer having a branched hydrocarbon group, a monomer having an alicyclic hydrocarbon group , a monomer containing a heteroaliphatic group or a heterocycle, and a monomer containing an aromatic ring.

In a first preferred embodiment, at least one monomer having a linear hydrocarbon group of general formula (I), (A) at least one fluorine-containing monomer represented by general formula (II), and/ Or (B) as a method of homopolymerizing or copolymerizing a monomer having a hydrophilic group, a known method can be employed, and examples thereof include a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, and the like.

In a second preferred embodiment, a method of homopolymerizing a fluorine-containing monomer of general formula (II), a fluorine-containing monomer of general formula (II) and (A) a monomer having a linear hydrocarbon group, and/or (B) ) a monomer having a hydrophilic group and/or (C) a monomer having a branched hydrocarbon group, a monomer having an alicyclic hydrocarbon group, a monomer containing a heteroaliphatic group or a heterocycle, and a monomer containing an aromatic ring As a method for copolymerizing at least one monomer selected from the group, a known method can be employed, and examples thereof include a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, and the like.

The form of the surface treatment agent of the present invention is not particularly limited and can be appropriately selected according to the application. For example, it can be used in the form of a solution or emulsion, preferably an aqueous emulsion. In the case of an aqueous emulsion, the copolymer produced by the emulsion polymerization method can be used as it is or after being diluted with water or a solvent.

When an emulsion polymerization method is employed, a desired ratio of each monomer is emulsified in water in the presence of a polymerization initiator, an emulsifier and an emulsifying aid, and the mixture is stirred at 50 to 90°C for 1 to 10 hours for copolymerization. .

When the surface treating agent of the present invention is an aqueous emulsion, it may contain an emulsifier, an emulsifying aid and a chain transfer agent. The emulsifier, emulsifying aid, and chain transfer agent may be the same compounds as those used in emulsion polymerization.

When the surface treatment agent of the present invention is a solution, the solvent is not particularly limited as long as the copolymer can be dissolved therein. For example, alcohols such as methanol, ethanol, and isopropyl alcohol, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate and butyl acetate, aromatic hydrocarbons such as toluene and xylene, ethers such as diethyl ether, and diethylene glycol monoethyl. Alkylene glycol monoethers such as ethers, alkylene glycol diethers such as diethylene glycol diethyl ether, tetrahydrofuran, and 1,4-dioxane can be mentioned. One type of these solvent components can be used, but two or more types may be blended in an arbitrary ratio and used.

Although the polymerization initiator is not particularly limited, for example, organic peroxides, azo compounds, persulfates and the like can be used. Water-soluble azo compounds are preferred, and for example, 2,2'-azobis[N-(2-hydroxyethyl)-2-methylpropanamide] is preferably used. The polymerization initiator can be used in an amount of 0.01 to 1% by mass, preferably 0.05 to 1% by mass, based on the total amount of monomers.

Anionic, cationic, and nonionic surfactants can be used as emulsifiers. Nonionic surfactants are preferred, and polyoxyethylene oxide addition type nonionic surfactants are preferred. Specifically, reaction products of polyethylene oxide with alcohols such as aliphatic alcohols and aromatic alcohols, alkyl ethers, C12-C18 alkylamine oleates, sorbitan monofatty acids and the like are used. The emulsifier can be used in an amount of usually 1 to 40% by mass, preferably 10 to 40% by mass, based on the total amount of the monomers.

Alcohol-based compounds and glycol-based compounds can be used as emulsifying aids. Specific examples of alcohol compounds include methanol, ethanol, isopropyl alcohol, and propanol. Examples of glycol compounds include ethylene glycol, polyethylene (N=2 to 4 or more) glycol, propylene glycol, polypropylene (N = 2 to 4 or more) glycols or their terminal monomethyl ethers, hexylene glycol, propylene glycol adducts of glycerin, and the like. Preferably isopropyl alcohol can be used. The emulsifying aid is generally used in an amount of 1-30% by mass, preferably 5-20% by mass, based on the total amount of the monomers.

In emulsion polymerization, a chain transfer agent can be used for molecular weight control, and alkylmercaptans such as N-octylmercaptan, N-dodecylmercaptan, TERT-dodecylmercaptan are preferably used.

When solution polymerization is employed, each monomer is mixed in a desired ratio, an appropriate amount of polymerization initiator is added, and the mixture is stirred in the presence of a solvent at a temperature of 60° C. to 100° C., for example, at about 85° C. for 3 to 15 hours. Polymerization is carried out by

The solvent is not particularly limited as long as it can dissolve the copolymer. For example, alcohols such as methanol, ethanol and isopropyl alcohol; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate and butyl acetate; Aromatic hydrocarbons such as toluene and xylene, ethers such as diethyl ether, alkylene glycol monoethers such as diethylene glycol monoethyl ether, alkylene glycol diethers such as diethylene glycol diethyl ether, tetrahydrofuran, and 1,4-dioxane. can be done. One type of these solvent components can be used, but two or more types may be blended in an arbitrary ratio and used.

(Surface treatment agent)
The surface-treating agent of the present invention contains rust inhibitors, catalysts, antibacterial agents, flame retardants, surfactants, antifoaming agents, thickeners, viscosity modifiers, leveling agents, Ultraviolet absorber, antiseptic, antifreeze, wetting agent, pH adjuster, stabilizer, antifungal agent, light stabilizer, weather stabilizer, neutralizer, matting agent, drying accelerator, foaming agent, non-adhesive agents, anti-deterioration agents, etc. may be added as appropriate.

The surface treatment agent of the present invention can be used as a releasing agent, a buffering agent, a water and oil repellent, an anti-resin adhesion agent, an anti-flux agent, an anti-fouling agent, an anti-moisture agent, and an oil barrier agent. The molding material released from the mold using this surface treatment agent is not particularly limited, but examples include urethane rubber, H-NBR, NBR, silicone rubber, EPDM, CR, NR, fluororubber, SBR, BR, and IIR. And rubber such as IR, urethane foam, epoxy resin, polyimide resin, polyamide resin, melamine resin, urea resin, polyurethane, silicone resin, alkyd resin, phenol resin, unsaturated polyester resin, vinyl ester resin and FRP (glass fiber reinforced Thermosetting resin such as plastic (GFRP), carbon fiber reinforced plastic (CFRP), aramid fiber reinforced plastic (AFRP), PP (polypropylene), PE (polyethylene), PVC (polyvinyl chloride), PS (polystyrene) ), PA (polyamide), polyester, polycarbonate, ABS resin, poly(meth)acrylic acid, polyacetal, polyvinylidene fluoride, polyphenylene sulfide, polyetherimide, polyetheretherketone, FRTP (glass fiber reinforced thermoplastic resin (GFRTP) , carbon fiber reinforced thermoplastic resin (CFRTP), aramid fiber reinforced thermoplastic resin (AFRTP)), and the like. In particular, it is useful as a release agent for molds for rubbers such as EPDM rubber and BR rubber and for resins such as FRP, as a buffering agent for resins such as FRP, and as a resin adhesion preventive.

FIG. 2 shows an embodiment in which the surface treating agent of the present invention is used as a buffer. In FIG. 2, the material X is not particularly limited, but for example, metals such as aluminum, SUS, and iron, resins such as PP, PE, and epoxy, rubber, FRP (fiber reinforced plastic), gypsum base material, and wooden base material. , composite materials, and the like. The material Y is not particularly limited, but examples include rubbers and resins. Specifically, rubbers such as urethane rubber, H-NBR, NBR, silicone rubber, fluororubber, CR, NR, SBR, IIR and IR. , composite materials, urethane foams, epoxy resins, phenol resins, unsaturated polyester resins, thermosetting resins such as FRP, and thermoplastic resins such as PP, PE, PVC, and PS.

When the surface treating agent of the present invention is used as a release agent for molds, for example, it can be used by applying it to the mold surface and drying it. The coating method is not particularly limited, and examples thereof include spray coating, brush coating, roll coater coating, and dipping coating. Examples of the drying method include air drying or heating to evaporate the solvent to form a film. The amount of non-volatile components in the release agent composition to be adhered to the mold is generally 0.01 to 10 G/M ² , preferably 0.1 to 10 G/M ² . Releasability is obtained.

In a preferred embodiment of the invention, the surface treatment agent can be used as a buffer for FRP. For example, autoclave molding, oven molding, or press molding of a prepreg in which carbon fibers (filaments, knitted fabrics, non-woven fabrics, etc.) are impregnated with a thermosetting resin or thermoplastic resin, or short fiber pellets in which carbon fibers are impregnated with a thermoplastic resin, In the process of injection molding and press molding of long fiber pellets and continuous fiber sheets, the surface treatment agent of the present invention is applied to the surface of the material (for example, molding die) in contact with FRP to prevent adhesion between FRP and the material. be able to. Thermosetting resins used in FRP include unsaturated polyester resins (UP), vinyl ester resins (VE), epoxy resins, and phenolic resins (PF), and thermoplastic resins include polycarbonate resins (PC). , polyethylene resin (PE), polyester resin, polyamide resin (PA), and vinyl chloride resin (PVC).

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these Examples.

Synthesis Example 1A
A 200 ML glass reactor was charged with 6 parts by mass of a fluorine-containing polymerizable monomer, (A) 30.6 parts by mass of behenyl methacrylate, (B) 2 parts by mass of 2-hydroxyethyl methacrylate, polyethylene glycol (N = 4 on average) mono Methacrylate (PE-200 manufactured by NOF Corporation) 2 parts by mass, lauryl mercaptan 0.2 parts by mass, polyoxyethylene alkylphenyl ether (Noigen EA-177 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 2 parts by mass, polyoxy 2 parts by mass of ethylene oleyl ether (EMULGEN 408 manufactured by Kao Corporation), 4 parts by mass of isopropyl alcohol, and 151.2 parts by mass of ion-exchanged water are added and emulsified and mixed using a high-pressure homogenizer, and the resulting emulsion is treated with nitrogen gas. was replaced with for 30 minutes.

After that, 20 parts by mass of a 1.5% by mass aqueous solution of 2,2′-azobis[N-(2-hydroxyethyl)-2-methylpropanamide] was added, and the internal temperature was gradually raised to 85° C., and the temperature was increased. It was held and reacted for 3 hours. After completion of the reaction, the mixture was allowed to cool to obtain an aqueous dispersion having a solid concentration of 22.3% by mass. The weight-average molecular weight of the resulting copolymer was measured by gel permeation chromatography (GPC) and found to be 62,000 (polystyrene was used as a molecular weight standard).

Synthesis Examples 2A-6A
A copolymer was produced in the same manner as in Synthesis Example 1A by changing the proportions of the fluorine-containing monomer, monomer A (monomer for component (A)), and monomer B (monomer for component (B)). The ratio of monomers and the species of monomers are as shown in Table 1. In Table 1, the numbers for the fluorine-containing monomer ratio in the copolymer represent % by mass, and F-1, A-1, A-2, A-3, A-4, B-1, B-2, B-3 The number of represents parts by mass.

Example 1A
The resulting aqueous dispersion was diluted with ion-exchanged water to 1% by mass, and a continuous release test was performed using BR rubber. Table 1 shows the results.

Examples 2A-3A, Comparative Examples 1A-3A
The continuous releasability was evaluated in the same manner as in Example 1A. Table 1 shows the evaluation results.

Synthesis Example 1B
A 200 ML glass reactor was charged with 4 parts by mass of a fluorine-containing polymerizable monomer, (A) 16.9 parts by mass of hexyl methacrylate, (B) 2 parts by mass of 2-hydroxyethyl methacrylate, polyethylene glycol (N = average 4) mono Methacrylate (PE-200 manufactured by NOF Corporation) 2 parts by mass, lauryl mercaptan 0.2 parts by mass, polyoxyethylene alkylphenyl ether (Noigen EA-177 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 2 parts by mass, polyoxy 2 parts by mass of ethylene oleyl ether (Emulgen 408 manufactured by Kao Corporation), 4 parts by mass of isopropyl alcohol, and 166.9 parts by mass of ion-exchanged water are added, emulsified and mixed using a high-pressure homogenizer, and the resulting emulsion is treated with nitrogen gas. was replaced with for 30 minutes.

After that, 20 parts by mass of a 1.5% by mass aqueous solution of 2,2′-azobis[N-(2-hydroxyethyl)-2-methylpropanamide] was added, and the internal temperature was gradually raised to 85° C., and the temperature was increased. It was held and reacted for 3 hours. After completion of the reaction, the mixture was allowed to cool to obtain an aqueous dispersion having a solid content concentration of 16.6% by mass. The weight-average molecular weight of the obtained copolymer was measured by gel permeation chromatography (GPC) and found to be 54,000 (molecular weight standard is polystyrene).

Synthesis Examples 2B-10B, Synthesis Examples 1C-14C
By the same method as in Synthesis Example 1B, the proportions of the fluorine-containing monomer, monomer A (monomer having a linear hydrocarbon group as component (A)), and monomer B (monomer having a hydrophilic group as component (B)) are changed. to produce a copolymer. The monomer ratio and monomer species are as shown in Tables 2, 4, 5 and 7. In Table 2, the numbers for the fluorine-containing monomer ratio in the copolymer represent % by mass, and F-11, F-12, A-11, A-12, A-13, A-14, B-11, B-12 The number of represents parts by mass.

Example 1B
The obtained aqueous dispersion was diluted with ion-exchanged water so as to be 3% by mass, and a release test was performed. An iron mold heated to 180 ° C. (molded product shape: cylinder with a diameter of 3.0 cm and a height of 3.0 cm) was sprayed with 2.0 G of the diluted aqueous dispersion with a spray gun ("Cup Gun W-" manufactured by Anest Iwata Co., Ltd.). 101"; caliber 1MM).

8.0 G of peroxide vulcanized rubber (EPDM) was placed in a mold and press-molded at 180° C. for 8 minutes. The release performance was evaluated by measuring the load when the molded article was taken out using a push-pull scale.

After the molding was taken out, the rubber was newly placed in the mold, press-molded in the same manner, and the continuous release property was tested. The number of mold release times until the load exceeded 50 N was defined as the number of continuous mold release times. Table 2 shows the results.

Examples 2B-4B, Comparative Examples 1B-2B
The releasability and continuous releasability were evaluated in the same manner as in Example 1B. Table 2 shows the evaluation results.

Example 5B
A 1% by mass solution of the copolymer of Synthesis Example 2B in tetrahydrofuran was prepared, and the solution was applied to a SUS test piece. After drying at room temperature, the contact angles of water and hexadecane with respect to the coated surface were measured at room temperature with a contact angle measuring device (Kyowa Interface Chemical Co., Ltd. DROPMASTER700). Table 3 shows the evaluation results.

Examples 6B-9B
The releasability and continuous releasability were evaluated in the same manner as in Example 1B except that the rubber type was changed from EPDM rubber to BR rubber. Table 4 shows the evaluation results.

The hexadecane contact angle of 74° is a very favorable numerical value, and it is considered that the fluorine-based surface treatment agent of the present invention has excellent releasability.

Example 1C
Using each fluorine acrylate shown in Table 5, a mold release test was performed according to the following evaluation conditions and evaluation method.
(1) Evaluation conditions Resin raw material: vinyl ester resin (FRP)
Molding machine: Hydraulic molding machine (70TON press machine)
Press pressure: 0.8-1.5 MPA
Pressing time: 2 minutes Evaluation mold: Chrome-plated iron test mold Mold temperature: 140°C
Amount of release agent applied: about 150G/ ^M2
Release agent applicator: Anest Iwata W-101 (cup gun, air pressure: 0.2 MPa)
(2) Evaluation method/release test
(1) A release agent was applied to the heated mold.
(2) A resin raw material was placed in a mold, and the resin raw material was cured under heat and pressure conditions.
(3) After curing the resin raw material, a suction cup was attached to the molded article, and the load when the molded article was peeled off from the mold was measured and used as the release force. A practical use level for the release force is 60N or less.
・Secondary workability (paintability) test
(1) Spray coating was applied to the surface of the molded product that was in contact with the mold.
(2) Allow to stand at room temperature for 24 hours until the coating is dry.
(3) A cutter was used to cut 11 vertical and 11 horizontal cuts (a total of 100 squares were made) on the coated surface.
(4) A piece of tape was applied to the notch.
(5) The tape was peeled off, and the presence or absence of peeling of the paint on the squares was confirmed.

In the evaluation of paintability, "◯" indicates "no paint peeling", "X" indicates "paint peeling", and "-" indicates untested.

In Synthesis Examples 1C to 12C, copolymers were produced in the same manner as in Synthesis Example 1B by changing the proportions of fluorine acrylate, alkyl acrylate, and hydrophilic acrylate.

Table 5 shows the results.

Examples 2C-3C and Comparative Examples 1C-2C
Using each fluorine acrylate surface treatment agent (Synthesis Examples 4C, 11C) and fluorine monomolecular compounds (F-21, F-22) shown in Table 6, the release test of the test piece was performed under the following evaluation conditions and evaluation method. I went there twice. Table 6 shows the evaluation results.
(1) Evaluation conditions Resin raw material: vinyl ester resin (FRP)
Molding machine: Hydraulic molding machine (70TON press machine)
Press pressure: 0.2 MPA
Pressurization time: 2 minutes Evaluation mold: Steel test piece SPCC-SB
Mold temperature: 140°C
Amount of release agent applied: about 150G/ ^M2
Release agent applicator: Anest Iwata W-101 (cup gun, air pressure: 0.2 MPa)
(2) Evaluation method (Fig. 1)
(1) A release agent was applied to the heated test piece.
(2) The resin raw material was placed between the test pieces and cured under heating and pressure conditions.
(3) After the resin raw material was cured, the load when the test piece was peeled off from the molded product was measured and used as the release force.

From the results in Table 6, it was confirmed that resin remained on the test piece (sticking to the mold) in Comparative Examples 1C and 2C using a monomolecular fluorine nonionic surfactant as a release agent, but Example 2C and 3C, no residual resin was observed on the test piece.

Example 4C
Using each fluorine acrylate shown in Table 7, a mold release test was performed according to the following evaluation conditions and evaluation method.
(1) Evaluation conditions Resin raw material: Epoxy resin Heating time: 40 minutes Evaluation mold: Chrome-plated iron test mold Mold temperature: 135 to 145°C
Amount of release agent applied: about 150G/ ^M2
Release agent applicator: Anest Iwata W-101 (cup gun, air pressure: 0.2 MPa)
(2) Evaluation method/mold release test
(1) A release agent was applied to the heated mold.
(2) The resin raw material was poured into a mold having a clip and heated to harden the resin raw material.
(3) After curing the resin raw material, the clip was pulled to measure the load when the molded product was separated from the mold, and this was defined as the release force. A practical use level for the release force is 60N or less.
・Secondary workability (paintability) test
(1) Spray coating was applied to the surface of the molded product that was in contact with the mold.
(2) Allow to stand at room temperature for 24 hours until the coating is dry.
(3) A tape was applied to the coated molded product surface.
(4) The tape was peeled off and the presence or absence of peeling of paint was confirmed.

In the evaluation of paintability, "◯" indicates "no paint peeling", "X" indicates "paint peeling", and "-" indicates untested.

Table 7 shows the results.

Claims (14)

A surface treatment agent containing the following polymer , wherein the surface treatment agent is a release agent :
general formula (I)

[In the formula, R ^1A is H or a methyl group. N is 1-24. ]
At least one monomer having a linear hydrocarbon group represented by
general formula (II)

[In the formula, RF is a group represented by the following formula (1) or (2).

R ^1B is a divalent group having 2 to 50 carbon atoms. ^R2 is H or a methyl group. ]
At least one fluorine-containing monomer represented by , and
Containing a monomer having a hydrophilic group as a repeating unit,
The proportion of the fluorine-containing monomer is 5 % or more and 15% or less by mass ,
A polymer, wherein the monomer having a hydrophilic group is a monomer having a hydroxyl group and/or a polyethylene oxide chain . A surface treatment agent comprising the following polymer, wherein the surface treatment agent is a buffering agent:
general formula (I)

[In the formula, R ^1A is H or a methyl group. N is 1-24. ]
At least one monomer having a linear hydrocarbon group represented by
general formula (II)

[In the formula, RF is a group represented by the following formula (1) or (2).

R. ^1B is a divalent group having 2 to 50 carbon atoms. R. ² is H or a methyl group. ]
At least one fluorine-containing monomer represented by, and
Containing a monomer having a hydrophilic group as a repeating unit,
The proportion of the fluorine-containing monomer is 5% or more and 15% or less by mass,
A polymer, wherein the monomer having a hydrophilic group is a monomer having a hydroxyl group and/or a polyethylene oxide chain. A surface treatment agent containing the polymer described in (II) below , wherein the surface treatment agent is a release agent :
(II) general formula (II)

[In the formula, RF is a group represented by the following formula (1) or (2).

R ^1B is a divalent group having 2 to 50 carbon atoms. ^R2 is H or a methyl group. ]
A polymer containing at least one fluorine-containing monomer represented by as a repeating unit, the proportion of the fluorine-containing monomer being 15% or more by mass. A surface-treating agent comprising the polymer described in (II) below, wherein the surface-treating agent is a buffering agent:
(II) general formula (II)

[In the formula, RF is a group represented by the following formula (1) or (2).

R. ^1B is a divalent group having 2 to 50 carbon atoms. R. ² is H or a methyl group. ]
A polymer containing at least one fluorine-containing monomer represented by as a repeating unit, the proportion of the fluorine-containing monomer being 15% or more by mass. The polymer comprises a fluorine-containing monomer represented by general formula (II) and the following monomers (A) and/or (B) and/or (C):
(A) a monomer having a linear hydrocarbon group
(B) a monomer having a hydrophilic group
(C) at least one monomer selected from the group consisting of a monomer having a branched hydrocarbon group, a monomer having an alicyclic hydrocarbon group, a monomer containing a heteroaliphatic group or a heterocycle, and a monomer containing an aromatic ring; 5. The surface treatment agent according to claim 3 , which is a copolymer containing as a repeating unit. 3. The surface treating agent according to claim 1, wherein the monomer having a linear hydrocarbon group represented by general formula (I) is one or two or more (meth)acrylates. (A) a monomer having a linear hydrocarbon group is represented by general formula (I)

[In the formula, R ^1A is H or a methyl group. N is 1-24. ]
The surface treatment agent according to claim 5 , which is one or two or more (meth)acrylates represented by. 6. The surface treating agent according to claim 5 , wherein (B) a monomer having a hydrophilic group is a monomer having a hydroxyl group and/or a polyethylene oxide chain. The surface treatment agent according to any one of claims 1 to 8, which is an aqueous emulsion. The surface treatment agent according to any one of claims 1, 3, 5 to 9 , which is a release agent for BR rubber. The surface treatment agent according to any one of claims 1, 3, 5 to 9, wherein the surface treatment agent is a release agent for BR rubber or EPDM rubber. The surface treatment agent according to any one of claims 1, 3, 5 to 9, wherein the surface treatment agent is a release agent for thermosetting resins. The following general formula (I)

[In the formula, R ^1A is H or a methyl group. N is 1-24. ]
A monomer having a linear hydrocarbon group represented by
(A) general formula (II)

[In the formula, RF is a group represented by the following formula (1) or (2).

R ^1B is a divalent group having 2 to 50 carbon atoms. ^R2 is H or a methyl group. ]
A fluorine-containing monomer represented by, and
(B) a monomer having a hydrophilic group,
wherein the proportion of the fluorine-containing monomer in the polymer is 5 % or more and 15% or less by mass ,
A surface treatment agent, wherein the monomer having a hydrophilic group is a monomer having a hydroxyl group and/or a polyethylene oxide chain ,
A method for producing a surface treating agent , wherein the surface treating agent is a releasing agent or a buffering agent . The following structural general formula (II)

[In the formula, RF is a group represented by the following formula (1) or (2).

R ^1B is a divalent group having 2 to 50 carbon atoms. ^R2 is H or a methyl group. ]
or homopolymerizing the fluorine-containing monomer represented by (A) a monomer having a linear hydrocarbon group and/or (B) a monomer having a hydrophilic group and/or (C) copolymerized with at least one monomer selected from the group consisting of a monomer having a branched hydrocarbon group, a monomer having an alicyclic hydrocarbon group, a monomer containing a heteroaliphatic group or a heterocycle, and a monomer containing an aromatic ring; and obtaining a polymer having the fluorine-containing monomer as a repeating unit, wherein the proportion of the fluorine-containing monomer in the polymer is 15% by mass or more ,
A method for producing a surface treating agent , wherein the surface treating agent is a releasing agent or a buffering agent .

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